Most pollutants in the Earth's atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene(1-8). Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed(5,9-11). Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain(12-14). Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations(9-11). Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.
Human exposure to pollutants from e-waste is an important scientific issue for their health effects. In this study, organohalogen pollutants in human serum sample from an e-waste dismantling site (n = 35) and a control site (n = 21), both located in Tianjin, Northern China, were analyzed using GC-ECNI-MS. Geometric mean concentrations of tetra- through hexa-BDEs, hepta- through nona-BDEs, PCBs, PBB-153, and DP in the exposure group were 2.77, 12.2, 44.1, 0.52, and 7.64 ng g(-1) lipid, respectively, which ranged from 1.5 to 7.4-fold higher than those in the control group through multivariate regression analysis, indicating that working and/or living in the e-waste site was associated with elevated body concentrations of these pollutants. Pollutants with low vapor pressures (i.e., hepta- through nona-BDEs and DP) were at significantly higher levels for e-waste dismantling workers than for local residents living around the e-waste site, suggesting higher exposure to these pollutants might exist for the occupational workers. (C) 2012 Elsevier Ltd. All rights reserved.